4-bromo-3,5-bis(dimethylaminomethyl)iodobenzene | 312304-54-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 4-bromo-3,5-bis(dimethylaminomethyl)iodobenzene
• 英文别名: 1-[2-bromo-3-[(dimethylamino)methyl]-5-iodophenyl]-N,N-dimethylmethanamine
• CAS: 312304-54-4
• 化学式: C₁₂H₁₈BrIN₂
• 分子量: 397.097
• InChiKey: OZYWYOZQDMAJFS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-bromo-3,5-bis(dimethylaminomethyl)iodobenzene 在 AgBF₄ 作用下， 以 二氯甲烷 、 丙酮 、 苯 为溶剂， 生成 [PtI(η1-C-C6H3(CH2NMe2)2-2,6-I-4)(PPh3)2]
  参考文献：
  名称：

  Bifunctional Pincer-type Organometallics as Substrates for Organic Transformations and as Novel Building Blocks for Polymetallic Materials

  摘要：

  The reactivity of the bifunctionalized ligand NC(Br)N\ 1 [IC6H2(CH2NMe2)(2)-3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, LI) at the C-aryl-1 or C-aryl-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt-II and Pd-II complexes were prepared that have a second functional group available for further reactions. These Pt-II and Pd-II complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported.

  DOI：

  10.1021/ja0177657
• 作为产物：
  描述：

  4-溴-3,5-二甲基苯胺 在 盐酸 、 potassium permanganate 、 dimethyl sulfide borane 、 甲基磺酰氯 、 三乙胺 、 sodium nitrite 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 、 叔丁醇 为溶剂， 反应 8.25h， 生成 4-bromo-3,5-bis(dimethylaminomethyl)iodobenzene
  参考文献：
  名称：

  Bifunctional Pincer-type Organometallics as Substrates for Organic Transformations and as Novel Building Blocks for Polymetallic Materials

  摘要：

  The reactivity of the bifunctionalized ligand NC(Br)N\ 1 [IC6H2(CH2NMe2)(2)-3,5-Br-4] has been studied as a versatile synthon for organic and/or organometallic synthesis. Chemoselective metalation (M = Pd, Pt, LI) at the C-aryl-1 or C-aryl-Br bonds was achieved by choosing the appropriate metal precursors. In this way a series of Pt-II and Pd-II complexes were prepared that have a second functional group available for further reactions. These Pt-II and Pd-II complexes were subjected to a wide range of organic and organometallic reactions, revealing the remarkable stability of their M-C sigma-bond and opening an easy route for the synthesis of mono- and (hetero)bimetallic building blocks. The scope of the chemistry of such building blocks shows that they are good candidates for use in the synthesis of dendrimers, bioorganometallic systems, or polymetallic materials. The X-ray crystal structures of the most representative complexes (2, 3a, 19, 20, and 24) are also reported.

  DOI：

  10.1021/ja0177657

文献信息

• Synthetic strategies towards new para-functionalised NCN-pincer palladium(ii) and platinum(ii) complexes
  作者：Martijn Q. Slagt、Robertus J. M. Klein Gebbink、Martin Lutz、Anthony L. Spek、Gerard van Koten

  DOI：10.1039/b204239h

  日期：——

  New para-functionalised NCN-pincer palladium(II) and platinum(II) complexes were synthesised, giving access to tuneable organometallic catalysts and sensor materials.

  新型对功能化的NCN钳式钯(II)和铂(II)配合物已被合成，使得可调谐的有机金属催化剂和传感器材料的制备成为可能。
• Synthesis and Properties ofpara-Substituted NCN-Pincer Palladium and Platinum Complexes
  作者：Martijn Q. Slagt、Gema Rodríguez、Michiel M. P. Grutters、Robertus J. M. Klein Gebbink、Wim Klopper、Leonardus W. Jenneskens、Martin Lutz、Anthony L. Spek、Gerard van Koten

  DOI：10.1002/chem.200305336

  日期：2004.3.19

  NCN-pincer palladium(II) and platinum(II) complexes [MX(NCN-Z)] (M=Pd(II), Pt(II); X=Cl, Br, I; NCN-Z=[2,6-(CH(2)NMe(2))(2)C(6)H(2)-4-Z](-); Z=NO(2), COOH, SO(3)H, PO(OEt)(2), PO(OH)(OEt), PO(OH)(2), CH(2)OH, SMe, NH(2)) were synthesised by routes involving substitution reactions, either prior to or, notably, after metalation of the ligand. The solubility of the pincer complexes is dominated by the

  多种对位取代的NCN钳夹钯（II）和铂（II）配合物[MX（NCN-Z）]（M = Pd（II），Pt（II）; X = Cl，Br，I; NCN- Z = [2,6-（CH（2）NMe（2））（2）C（6）H（2）-4-Z]（-）; Z = NO（2），COOH，SO（3） H，PO（OEt）（2），PO（OH）（OEt），PO（OH）（2），CH（2）OH，SMe，NH（2））是通过涉及取代反应的途径合成的，或者在或者，特别是在配体金属化之后。对夹配合物的溶解度受对取代基Z的性质支配，这使得几种配合物是水溶性的。通过（195）Pt NMR光谱和DFT计算研究了对位取代基对金属中心电子性能的影响。（195）Pt化学位移和计算得出的铂上自然电荷均与sigma（p）Hammett取代基常数线性相关，因此，可以预测预先设计的钳夹复合物的电子性质。对-PtI基团本身的sigma（p）值在甲醇中确定为-1
• Non‐Tethered Organometallic Phosphonate Inhibitors for Lipase Inhibition: Positioning of the Metal Center in the Active Site of Cutinase
  作者：Cornelis A. Kruithof、Harmen P. Dijkstra、Martin Lutz、Anthony L. Spek、Maarten R. Egmond、Robertus J. M. Klein Gebbink、Gerard van Koten

  DOI：10.1002/ejic.200800654

  日期：2008.10

  conversion to the protein-pincer metal complex hybrid was obtained in 48 h. The NCN-pincer metal phosphonic acid derivatives (3, 4) appeared to be inactive as cutinase inhibitors. In contrast to our previous work which entails propyl tethered phosphonate esters connected to pincer metal complexes, the presented strategy allows positioning of metal complexes inside the active site of lipases. This opens up

  合成了有机金属 NCN 钳配合物，带有对硝基苯基膦酸酯或直接连接到钳配合物芳环的膦酸基团。测试这些化合物作为脂肪酶角质酶的共价抑制剂。在 NCN-钳状铂膦酸对硝基苯酯 2 与角质酶的化学计量反应中，在 48 小时内获得了 94% 向蛋白质-钳状金属复合物杂化物的转化。NCN 钳形金属膦酸衍生物 (3, 4) 作为角质酶抑制剂似乎无活性。与我们之前的工作需要连接到钳状金属配合物的丙基系膦酸酯相比，所提出的策略允许将金属配合物定位在脂肪酶的活性位点内。
• Synthesis and characterization of bioorganometallic conjugates composed of NCN-pincer platinum(II) complexes and uracil derivatives
  作者：Toshiyuki Moriuchi、Shunichi Noguchi、Yuki Sakamoto、Toshikazu Hirao

  DOI：10.1016/j.jorganchem.2010.10.018

  日期：2011.3

  the formation of the NCN-pincer platinum(II) complex bearing the 6-ethynyl-1-octyluracil moiety. The NCN-pincer platinum(II) complex bearing the furanopyrimidine moiety was obtained by the reaction of the NCN-pincer ligand bearing the furanopyrimidine moiety with [Pt(tolyl-4)2(SEt2)]2. The single-crystal X-ray structure determination of the NCN-pincer platinum(II) complex bearing the furanopyrimidine

  NCN钳式铂（II）配合物作为有机金属化合物和尿嘧啶衍生物作为核碱基的共轭被证明可以提供相应的生物有机金属。合成了带有6-乙炔基-1-辛基尿嘧啶，5-乙炔基-1-辛基尿嘧啶和呋喃并嘧啶部分的NCN-钳位配体。在晶体状态下，发现带有6-乙炔基-1-辛基尿嘧啶部分的NCN-钳位配体通过尿嘧啶基团之间的分子间氢键形成氢键二聚体，该分子间通过尿嘧啶和尿嘧啶之间的π-π相互作用连接。 NCN-夹子配体的苯部分。带有6-乙炔基-1-辛基尿嘧啶部分的NCN-钳位配体与[Pt（tolyl-4）2（SEt 2）] 2的反应导致形成带有6-乙炔基-1-辛基尿嘧啶部分的NCN-钳位铂（II）配合物。通过使带有呋喃并嘧啶部分的NCN-钳位配体与[Pt（甲苯基-4）2（SEt 2）] 2反应，得到带有呋喃并嘧啶部分的NCN-钳位铂（II）配合物。对具有呋喃并嘧啶部分的NCN钳式铂（II）配合物的单晶X射线结构测定表
• Shape-Persistent Nanosize Organometallic Complexes:  Synthesis and Application in a Nanofiltration Membrane Reactor
  作者：Harm P. Dijkstra、Cornelis A. Kruithof、Niek Ronde、Rob van de Coevering、Diego J. Ramón、Dieter Vogt、Gerard P. M. van Klink、Gerard van Koten

  DOI：10.1021/jo0257602

  日期：2003.2.1

  Shape-persistent multi(NCN-palladium and/or -platinum) complexes having one- (5 and 6), two- (1 and 2), and three-dimensional (3 and 4) geometries were prepared in moderate to good yields. Two different approaches were used to construct the multimetallic materials: (i) the construction of the multisite ligands followed by the permetalation step and (ii) selective and mild one-pot coupling of monometallic

  制备具有一（5和6），两（1和2）和三维（3和4）几何形状的形状持久的多（NCN-钯和/或-铂）络合物，其产率中等至良好。两种不同的方法被用于构建多金属材料：（i）多位配体的构建，然后进行过金属化步骤；（ii）单金属结构单元选择性和温和的一锅偶联到多功能的形状持久性有机核分子上。第一种方法用于制备呈palpalated和/或镀铂的tris-（2）和bis（NCN-pincer）（5）复合物，而第二种方法则提供呈palpalated和镀铂的octakis-（3）和十二烷基（NCN-pincer ）（4）配合物。对复合物1-6进行纳滤（NF）实验，以研究刚性和几何形状对NF膜保留这些分子的影响。为此，使用了相应的（NCN-Pt-X）（n）（）配合物（1c-4c，5和6），因为将这些配合物暴露于溶液中的二氧化硫中导致形成鲜橙色配合物，使用紫外/可见光谱法准确测定渗余液和渗透液中1-6的浓度。使用MPF-60（MWCO